Morphinans, including N-alkylated morphinans and normorphinans, are important pharmaceuticals, typically used as analgesics or drug/alcohol cessation agents. Substituted morphinans, such as 6-amino derivatives, may be useful therapeutically because they have higher efficacy, greater potency, and/or may function as prodrugs. Although several methods for forming 6-amino morphinans from 6-keto morphinans have been reported in the literature, none provides the stereoselective synthesis of 6-alpha-amino epimers in good yield. Furthermore, the existing methods require the use of highly reactive reducing agents and/or hydrogen gas. There is a need, therefore, for simple, mild, and efficient processes for the preparation of 6-alpha-amino morphinans of high enantiomeric purity.